Water insoluble azodyestuffs



Patented Aug. 18, 1931 UNITED srATss; "BATE ,1

RICHARD HERZ, 0F FRANKFOR'I-ON-THE-MAIN, AND MAX SGHUBERT, OF FRAHKFORT}ON-TI-IE-MAIN-FECHENHEIM, GERMANY, ASSIGNOR S 'IOGENERAE'JwQNILINEjWOQKS; ING, OF NEW YORK, N. Y., A CORPORATION OFDELAWARE i -11121; 7

- WMERINSQIJEIBLE dyestufi's of the general formula:

filed September'1'3, 1929, relates to new azowherein R stands, for anaromatic residue Whose hydrogen atoms may be. substituted or not, R foran isocyclie residue Whose hydrom gen atoms may beisubstituted or notand aryl for an aryl residue Whose hydrogen atoms may besubstituted'or'notf Our presentinvention relates to certain embodimentsof'the' above mentioned series of dyestufis, more particularly itrelates; to new dyest-ufis gorrespondingto the formula whereinarylnieans a residueoithe'benzene or naphthalene series they neanshydrogen w ino-Nnwer l;

vvhioh dyestuffs yield valuable oolorlakes o when mixed with the usualsubstrata and dye the vegetable fiber valuable blue to bluish blackshades of a very good fastnessivvhen produced on the fiber. The newdyestuffs are obtainable bycombining in substance ori 45 on asubstratum, particularly on the vegeta Deceirrherii' i;

aeon-densatidrfifirod tor" he yin-ef wherein Z" "means hydrogen or anamino"- 'group, with an arylaini'de of 2.i-l-hydroxynaphthoic acid. Whenusing the N=nitrosoderivatives of the iforesajid diazoor tetra-'zooompounds, the primary arzodyestufisiob- 'tain edfdyerecl-lilge garnetto olaret shades fand'tihe nitrosogroupis spflit'oif by treatment th fap ii i in e it d s w l 'Wltill addit on, of a: reduc ng agent accordingLaslra et al'.,*ffiled Nateean, wherebluetobluisll' blaok'shades. j" l HIn orderto further illuStrateOur invention,

the followin'g exainples arefgiven; all ten;-

per'at-ures being' in bentigra;de;degrees, buta've Wish it to beunderstood, that we are; net l-i initedto theparticular pro'duetsiiorea- 1011;; jw d i e e i nsdflir ie Wellf boiled cotton fyarn is impi egnfati 5d "with a solution 'prepared by di'sso'lviriglO g'r's.

of 2.3 hydroxynaphthoyl 4 chloroai iline with additiono'f 2o cemz-oiTurkey red en, 20

- com ofia caustiosodasolution of 34 l3tin 500' grs. of'boiling waterand made 'upto one liter. After having been Well squeezed the thusimpregnated materialis developed with a T tetrazosolutiom prepared asfollows f 1 58 grs; o f bis-v(4(4aininophenyl '-2.fi-n'aphthylenediamin'e-are stirred with 20 grs.iof hot Water, 5 ccm ohydrochlprid acid of 20 are addedand thermigctur is, diluted with about209 grsrof ice water. Then thesolu:

"ble 'fibersatlie d am.- m tetrioeom m neer lil) of j ater is iadded atabout 1015 andafter is made up with cold water to one liter andneutralized with sodium acetate before using it. After having beendeveloped the dyed material is wellsqueezed, washed and soaped in aboiling soap bath. The dyestuif thus formed corresponds probably to theformula Example 2 Well boiled cotton yarn is impregnated with a solutionof 4 grs. of 2.3-hydroxynaph- The 6 aminophenyl (4-aminophenyl) 2-naphthylamine used as starting material may be prepared by acting withEZ-hydroxy- 6-phenylaminonaphthalene on para-phenylenediamine in thepresence of a bisulfite solution or by treating the 6-phenylamino-2-naphtholcarboxylic acid with paraphenylenediamine in presence of abisulfite solution, whereby the carboxylic acid group issplito-ff. V A Qg r We claim: j a y 1. As new compounds azodyestuffs correspondingprobably to the. formula:

wherein aryl means a residue of the benzene or naphthalene series and Ymeans hydrogen or the grouping thoyl-B-naphthylamine, 1O ccms. of Turkeyred oil and 8 ccms. of a caustic soda solution of 34 B. in the liter andwell squeezed.

43 parts of G-phenylamino-(y-aminophenyl) -2 -naphthylamine arediazotized with 21 parts of sodium nitrite in a hydrochloric acidsolution, whereby simultaneously the N-nitrosocompound is formed. Thenthe liquor is diluted to a concentrationof a hundredth molecule in theliter and sodium carbonate is added until the solution shows only afeeble acid reaction. The impregnated cotton yarn is developed in thissolution of the nitrosodiazocompound thus formed and rinsed first withcold andthen with hot water.

In this manner a red like garnetdyeing is obtain-ed. I

When aftert-reating this dyeing for a short time at about 80-85 with aliquor containing for instance 5 grs. of carbonate of soda, 3 grs.ofsoap and 0,5 grs. of anhydrous sodium sulfide in the liter and rinsingthe ima- 1 terial bright bluish black shades are ob tained. The dyestuifthus produced corresponds probably to theformula:

- 7011 which dyestuffs :yieldvaluable color lakes ;when;mixed with 'theusual substrata and dye the vegetable fiber valuable blue to bluishblack shades of a very good fastness when produced on the fiber.

2. As new, compounds azodyestuifs'cdrra sponding probably to theformula:

N's O eeK wherein aryl means a'residue of the benzene or naphthaleneseries, which dyestufi's yield valuable color lakes when mixed with theusual substrata and dye, the vegetable"fiber valuable blue to bluishblack shades of a very good fastness when produced on the fiber.

3. As new compounds azodyestufi's corresponding probably to the formula:

- NHON=Ng O OH o-NH-ar wherein aryl means a residue of the benzene V ornaphthalene series, which dyestufli's yield Valuable color lakes whenmixed with the usual substrata and dye the vegetable fiber valuable blueto bluish black shades of a very good fastness when produced on thefiber. V

4. As a new compound the azodyestufi' corresponding probably to theformula:

which dyestufl dyes the Vegetable fiber bright bluish black shades of agood fastness when produced on the fiber.

5. Materials dyed with dyestuffs as claimedin claim 1.

- 6. Materials dyed with dyestufis as claimed in claim 2. V

7. Materials dyed with dyestuffs as claimed in claim 3. r

8. Materials dyed with the dyestufi' as r claimed in claim 4.

In testimony whereof, we afiix our signaltures.

RICHARD HERZ. MAX SCHUBER-T.

